Linoleum binding composition



Patented July 15, 1952 In the preparation of linoleum, it is usual toprepare a tough-binding composition which op- I tionally is mixed with afiller or the like'and formed into a linoleum sheet. Accordingto theusual -procedure, there is prepared the binding agent, known in the artas a linoleumcement, which "generally consists of a siccative oil-resincomposition, optionally together with; suitable and desired modifiers.As the oil; there is empmyeq any of the well-known thickeneddrying or'serni-dryin'goils such as, for example; raw, blown, bodied or modifiedsoybean 'il,'linseed oil, or the like, raw, blown, bodied or dehydratedcastor'oil, or tlijelilregand in combination with this oil a resin,- forexample,- a natural 'or synthetic resirr such asalkyd-resins, phenolaldehyde resins, rosinand 'modified rosinsg 'ester gums; and othernatural and synthetic resins which are readily available. Y

1 According tothe conventional procedure, the siccative oilbe preparedor treated, for example, bythe appropriate process such as mildoxidationor the like hm a desired consistency is" obtained afterwhich-the resin -is blended therewith "and the composition mixed ormilled, optionally together with fillers, pigments, and the like,'andthe composition is then calenderd; In such prior procedures; arelatively long curing operation'is required, for example, after the I2,603,572 D QQMR SII ON Frank' G; Oswald; Wilmington, Den, eseigiioi {toi Hercules Powder Company, Wllmington, Del.-,*a-

' corporation ofDelawar-e 5 w Nonre 'ing'; Application M'ai14,1949,'

; 7 Serial No. 93,427"'t' 1 i i jcomm. (o1. 106-'-222)' calenderingstep, a curing. period generally. ex-

tending for a period of about three weeks at the end of which time ahard-wearing, rugged sure {ace covering composition results;- I ,m-Nowinaccordance with thepresent invention, there is prepared a novel linoleum'cementcomposition comprising binding materials suchas a siccativeoil-resin blend, now modified with an 'alkylated hydroxyalkylcellulose,'said composition heme characterized by a significantlyshortened curing period. A highly satisfactpry compo'sif tion may beprepared by blending together a siccative oil and a resin' compatiblewith organo soluble cellulose ethers'and, during the mixing or millingthereof, adding to thecompo'sition an alkylate'd hydroxyalkyl celluloseether such as, for example, an ethylated hydroxyethyl cellulose; afterwhichthere may be incorporated fillers, pigments and further additivesas 'desiredaiid'the mixture 'calendered to the required thicknessjandcured in a significantly shorter'tiin'e tha'nisf-re' quired' for "thecomposition notjcoritaining': the cellulose-etheri v tblue'ne perl'part'ethyl alcohol M After the thus eompound'e linoleum pomp} h Thegeneral nature of the invention having been set forth; the followingexamples are pre; sented "in illustration but, not in limitation'oif thes? thereof -"f V l v Exarri'plel- V r k 3; 4, .rn xure was preparedof3Q80 parts of lin e 9' Iain-1 541 Par s l ee ndgast eam 1: a r Pas hrougth mixture i m c anile iiation for allows-M2 0 F- n nt .th siccatiye oilreached a consistencywhere the'roil h ll d uffiq s tly J 9. c n toqthera it Atthe end of this timegthere was addedtogthe mpqs iiqn 920.11%190m; m iens o h ro 9 1 1 5 e ter o a. PQlX I GEiZ Q tw nk lllplifidmne Vder the trade nameigi'olyepale Ester .No;.--:-1-,;( by he-:Herwle Pqwmpan a d'theistr am s ewe 19 i nued. er ih 9 h' r e additional m e and tcon ist nc ofthermixe FBI? We? sl hzl abe u h-e i cb e nediwh ch .194 5?lins$-bQ-.t 1 itatort th ztime t r We? t add d t th mix ure e ylatecl hyz by :Q l1 l0se,. n. o nt ii a'l. t ota e ultin ix he et at d h l x ei el l se b n ed ya lend n e te iz r t r s:Qf250 0F27 n is; blen -t ingoperationgthe ethylated hydroxyethyl H lose. was first; milled on a;two-roll: mill;v

was t softened and the siccative oileresin gblend was added tothejmil-l; .insmalrportiqns; overra period ofa few; minutes, Theresulting compo-1 sition was i-milled t for 1Q minutes and gt he rollsfi e e 1- ool oneto 2 0. 3: end the to a temperature as pool as couldbeniain tained with cold water. ,Under these conditions e i h'. nt m d mlling d ired: fil erzand pigments were added over. a lQ-minute perlodand the composition milled for an additional '20 minutes ,to insureintimate mixture of ,the components; after: which the: lowtemperaturei-roll was heated slightly and the material sheetd therefrom.In the preparation;ofxthis vcomposition, there were employed .3150 partsof :the sic cative; oil-resin mixturef3300" parts wood flour, 2520,parts York whiting; 780 parts rutile titanium dioxide and 350' parts ofan ethylatedhydroxy ethyli..cellulosei having 'a degree of hydroxyethylsubstitution 0f" 0.6 7 'a deg-re'e 'of etlid I, tutio'n" 'of 2.58 and asolution vis'cosit-y f as 5 solution in a 'sdlven't l eons-i em. 2 hee-e6 h tdn ll W l$ ender H c Q and cured at 170 F. At the elld of 11dlys,

Ezcwmple 2 The procedure of Example 1 was reteatagem ploying the formulaof Examplel with the excep tion that FF wood rosin wassubstituted forthPoly-pale Ester No. 1. After a curing time of 11 days, the linoleum hada residual, indentation of slightly less than 4% and was cons'idered'.to"be" 4 gree of hydroxyalkyl substitution between about 0.3 and about1.0 hydroxyalkyl group per anhydroglucose unit and a degree of alkoxysubstitution of at least 2.4 alkoxy groups per anhydroglucose unit. Itis presently believed and understood that a certain degree of alkylationof the hydroxyalkyl groups may occur, butit is-not desired to limitthisinvention to the presence of such modified side chains of the cellulosemolecule "imasmuch as highly useful compositions may bereparedbyprocedures which cannot yield such 'odifi'cation ofthe sidechains. General correla- "tion 'ofv degree of substitution withproperties of theresulting linoleum composition indicates that with'anincreasing degree of substitution such as,

- for example, an hydroxyethyl substitution of 0.98

cured whereas a similar composition containing no ethylated hydroxyethylcellulose required a.

curing time of 21 days toreach this same degree ofcure.

7 In the preparation of a linoleumaccording to a parallel procedure, thevethylat'ed hydroxyethyl cellulose was replaced with an ethyl cellulosehavmg a softening temperature somewhat higher than 150 C. At a millingtemperature below 300 F. roll temperature, this ethyl celluloserdid notsoften sufficiently to permit its milling together with the siccativeoil-resin composition and ata'roll temperature of-320? F., when thesiccative oil-resin composition was mixedtherewith, the cement cured onthe rolls beforeall the filler andpigmentcould-be added thereto.1 Y-Indetermining the degreeof cure possessed by a linoleum-"cornposition,"'andin measuring the p and an ethoxylsubstitutionsubstantially higher than 2.5, imparts to the composition a higherfiexibility'anda greater softness.

Likewise, when proceeding according to this invention, it has generallybeen found that; the increased rate of curingimparted to,th'ecomposition is more pronounced with theaddition of greaterquantities of the alkylated hydroxyalkyl cellulose incorporated therein;For example, when about alkylated hydroxyalkyl cellulose is employed, anintermediate curingperiod re sults,;being somewhat less than thecuringrtime for the unmodified cement but greater than the curing timefor the composition containing about 10% ether, whereas a cementcontaining about cellulose ether will have a significantly shorter cure.In general, it is found that for an optimum balance of properties suchas flexibility, softness, curing speed and the. like, it is advisable toemploy an amount of the cellulose ether up to about 50%, basedv on thetotalcomposition, and

on aspot'otmeasured thicknesswithina 5 -'second period andat 'theend'of'the 5-second period, the

major load i's-ap'plied for seconds and the load immediately released.Afterg6 0 minutes, the residual indentation is d'etermined'as the percent of original thickness at the test spot. For the V purposes ofc'omparative tests, a composition was considered to be satisfactorilycured when are- 's'idual indentation of about 4% is measuredin this testY i I The alkylated hydroxyalkyl cellulose is selected from the group oflower 'alkyl'compoundsandis chosen'to give an optimum balanceof'properties tothelinoleum product; Thus, in the examples there hasbeendisclosed-an ethylated hydroxyethyl cellulose which has been shown to"impart desirable properties to the product .It will be understood, ofcourse, that there may be employed other alkylated' hydroxyalkylcompound's and, general, where a relatively hard linoleum ,product is tobe for-med, it is preferred to employ the'lower members of these alkylclasses-such as, for example,'methy1ated hydroxyalkyl celluloses,alkylatedhydroxymethyl; celluloses, .ethylated' hy- I ethylcellulcsesprsimilarv lower members of .th class- Thepreferred alkylated-hydroxyalkylremiss Wei l}??? w n r d r i a i s adsaddition of the ingredientscontemplates the introduction of thealkylated hydroxyalkylcellu-e loseafter thesiccative oil has attained thefdesired consistency.,'I'hus,;for example, when the siccative oil is treated by blowing orthe like, it i preferred to carry out the-blowing opera: tion prior totheaddition of the valkylated hydroxyalk-yl cellulose according toprocedures known in the art, and when the alkylated hydroxyalkylcellulose is' blended with the 'siccative oil or siccativeoil-resincomposition "at the 'desired consistencygthe composition thus producedhas a shortened curing *time' as compared with the time which may beprodiic'ed without" the presence of thecellulose derivative; However, itwill'be understood that in the blending andmix ing of tl e'com'p'onentsof the new linoleum composition there may be employed any of theblendstutlon of at least about 2.4 groups per anhydrolucose unit.

2. A binding composition comprising a blend of a resin and a siccativeoil and not more than about 50% based on the total weight of thecomposition of an ethylated hydroxyethyl cellulose ether having a degreeof hydroxyethyl substitution between about 0.3 and 1.0 and ethylsubstitution of at least about 2.4 groups per anhydroglucose unit.

3. A binding composition comprising a blend of a resin and a siccativeoil and between about 5 and about 25% based on the total weight ofthecomposition of an ethylated hydroxyethyl cellulose ether having adegree of hydroxyethyl substitution between about 0.3 and 1.0 and ethylsubstitution of at least about 2.4 groups per anhydroglucose unit.

4. A binding composition comprising a blend of a natural resin and asiccative oilrand between about 5% and about 25% based on the totalweight of the composition of an alkylated hydroxyalkyl cellulose etherhaving a degree of hydroxyalkyl substitution between about 0.3 and 1.0and alkyl substitution of at least about 2.4 groups per anhydroglucoseunit.

5. A binding composition comprising a blend of a. rosin and a siccativeoil and between about 5% and about 25% based on the total weight of thecellulose ether, having a degree of hydroxyethyl substitution betweenabout 0.3 and 1.0 and ethyl substitution of at least about 2.4 groupsper .anhydroglucose unit.

FRANK G. OSWALD.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,877,856 Hagedorn et a1. Sept.30, 1932 2,388,764 Reichel et a1. Nov. 13, 1945 OTHER REFERENCESCellulose and Cellulose Derivatives, Emil Ott, Interscience Publishers,Inc., N. Y., 1943, pn 800 and 801.

1. A BINDING COMPOSITION COMPRISING A BLEND OF A RESIN AND A SICCATIVEOIL AND NOT MORE THAN ABOUT 50% BASED ON THE TOTAL WEIGHT OF THECOMPOSITION OF AN ALKYLATED HYDROXYALKYL CELLULOSE ETHER HAVING A DEGREEOF HYDROXYALKYL SUBSTITUTION BETWEEN ABOUT 0.3 TO 1.0 AND ALKYLSUBSTITUTION OF AT LEAST ABOUT 2.4 GROUPS PER ANHYDROGLUCOSE UNIT.